Download Chapter 15: Thermal Properties of Matter

Chapter 15 Lecture
Chapter 15:
Thermal
Properties
of Matter
© 2016 Pearson Education, Inc.
Thermal Properties of Matter
10^11 stars in our Milky Way
Goals
• Relate the macroscopic properties to the
microscopic properties
• Gain an understanding of the thermal
properties of matter
• Consider various phases of matter: gas, liquid,
and solid and conditions under which they
occur
Avogadro's Number
• A number to describe a set count of
atoms, like "dozen" is a standard set
for eggs.
• Because atoms are so small, it must
be a huge number: 6.022 1023.
• To put that number in perspective,
count all the stars. That number
would be approximately 100 billion
(1.0 1011).
• It would take a trillion (1.0 1012)
Milky Way galaxies to contain as
many stars as there are particles in a
mole. Again, because atoms are tiny.
© 2016 Pearson Education, Inc.
Macroscopic parameters: pressure, volume,
temperature, and mass.
1 mole each of several
familiar substances
Microscopic parameters: speeds, kinetic energies,
momentum and masses of individual molecules.
Ideal gas can relate the macroscopic and
microscopic parameters.
Phases of matters: gas, liquid, and solid.
Use the mole as the unit to describe the quantity of
material (rather than mass).
Mass of an H-atom: 𝑚𝐻 =
𝑀𝐻
𝑁𝐴
=
𝑔
𝑚𝑜𝑙
𝑎𝑡𝑜𝑚
6𝑥1023
𝑚𝑜𝑙
1.008
𝑔
= 1.67𝑥10−24
𝑎𝑡𝑜𝑚
Mass of an 𝑁2 -atom: 𝑚𝑁2 =
𝑀𝑁2
𝑁𝐴
=
𝑔
𝑚𝑜𝑙
𝑎𝑡𝑜𝑚
6𝑥1023
𝑚𝑜𝑙
(16∗2)
𝑔
= 53𝑥10−24
𝑎𝑡𝑜𝑚
1 mole (1 mol) is the amount of a substance
that contains as many molecules or atoms
as there are inside 0.012kg of carbon 12
Avogadro’s number 𝑁𝐴 = 6.022𝑥1023
molecules/mole. Molar mass 𝑀 of a
substance is the mass of 1mol.
𝑀 = 𝑁𝐴 ∙ 𝑚
𝑚𝑎𝑠𝑠 𝑜𝑓 𝑎 𝑠𝑖𝑛𝑔𝑙𝑒 𝑚𝑜𝑙𝑒𝑐𝑢𝑙𝑒
𝑚 𝑇𝑜𝑡𝑎𝑙 = 𝑛 ∙ 𝑀
(Total mass=number of mol X molar mass)
Clicker - Questions
Which has more atoms: a one gram sample of carbon-12, or a one gram
sample of carbon-13?
a) carbon-12
b) carbon-13
Equations of state with state variables
Ideal gas equation:
𝑁
𝐽
𝑝𝑉 = 𝑛𝑅𝑇 [J = 𝑚2 𝑚3 = 𝑚𝑜𝑙 𝑚𝑜𝑙.𝐾 𝐾]
𝑅 = 8.3145
𝐽
𝑎𝑡𝑚
= 0.08206 𝐿.
𝑚𝑜𝑙. 𝐾
𝑚𝑜𝑙. 𝐾
𝑚𝑡𝑜𝑡𝑎𝑙
𝑚𝑡𝑜𝑡𝑎𝑙 𝑝𝑀
𝑝𝑉 =
𝑅𝑇 → 𝜌 =
=
𝑀
𝑉
𝑅𝑇
Remember 𝑚𝑡𝑜𝑡𝑎𝑙 = 𝑛 ∙ 𝑀 and 𝑀 = 𝑚𝑜𝑙𝑎𝑟 𝑚𝑎𝑠𝑠
For a constant mass (number of moles) of an ideal gas
𝑝1 𝑉1 𝑝2 𝑉2
=
= 𝑛𝑅 = 𝑐𝑜𝑛𝑠𝑡𝑎𝑛𝑡
𝑇1
𝑇2
STP (standard temperature and pressure):
0°𝐶 = 273𝐾 and 1 atm = 1.013𝑥105 𝑃𝑎
How large is a container to keep 1mole of gas at STP?
𝐽
𝑛𝑅𝑇 1𝑚𝑜𝑙 ∗ 8.314 𝑚𝑜𝑙. 𝐾 ∗ 273𝐾
1000𝐿
3
𝑉=
=
=
0.0224𝑚
∗
= 22.4 𝐿
𝑝
1.013𝑥105 𝑃𝑎
1𝑚3
PV-diagrams
Isotherm = (same temperature)
curve representing pV-behavior
at a specific temperature
Critical temperature = temperature
above which material does not
separate into two phases. It goes
smoothly without a phase transition.
Not ideal gas
Critical
Pressure
The area under a pV-curve represents the
work done by the system during a change
in volume equivalent to heat transfer and
the change of the internal energy.
PT-phase diagram
A graph which indicates what phase
occurs at a particular p and V
(Line a)  horizontal = constant pressure
reducing T yields: vapor, liquid, and solid phases
(Line b)  vertical = constant temperature
increasing p yields: vapor, liquid, and solid phases
(Line s)  horizontal = constant
pressure sublimation or direct transfer
of solid to liquid (no vapor phase).
Example: dry ice  carbon dioxide
Triple point = all three phases coexist at a
unique pressure-temperature combination.
Critical point= distinction between liquid and
gas disappears (properties change gradually)
4 steps:
1. Find  p /collision
2. Find # of collisions
Aim: derive pressure in the molecular picture
3. Find force/area
Atoms sizes ≈ 10-10 m
4. Find p and relate to ideal gas law
Kinetic theory of an ideal gas
Elastic collision of a
molecule with the wall
Largest molecule sizes ≈ 10-6 m
In gas molecules are in motion.
In solids molecules vibrate
around centerss.
In liquids molecules vibrate with
more freedom in movement.
NaCl
silicon
1. Kinetic molecular theory of an ideal gas:
assume all molecules to have the same velocity
∆P = m vx − −mvx = 2mvx
2. The number of collisions with wall (area A)
during ∆t is
1N
#=
(A|vx |∆t)
2V
1N
NAmvx 2 ∆t
∆Px =
A vx ∆t 2mvx =
2V
V
Small ‘p’  pressure
Large ‘P’  momentum
3.
∆𝑃𝑥
∆𝑡
=
𝑁𝐴𝑚vx 2
𝑉
𝑑𝑃
= 𝐹;
= 𝑚𝑎 = 𝐹
𝑑𝑡
Remember Newton’s law
Note: Parallel
Velocity
Does not
Change!
𝑝=
𝐹
𝐴
=
𝑁𝑚𝑣x 2
𝑉
 𝑝𝑉 = 𝑁𝑚𝑣x 2
Kinetic energy of gas molecules
Aim:The average translational kinetic energy
of a molecule depends only on T, not p or V
Express 𝑣x 2 in terms of the average in 𝑣 2 of all molecule
1
𝑣av 2 = 𝑣𝑥av 2 + 𝑣𝑦av 2 + 𝑣𝑧av 2 = 3𝑣𝑥av 2 (no distinction between x, y, and z) 𝑣𝑥 2 = 3 𝑣 2
1
2 1
2
2
2
𝑝𝑉 = 𝑁 𝑚𝑣
=
𝑁 ( 𝑚𝑣 )
=
𝐾
3
3 2
3 𝑡𝑟
𝑛𝑢𝑚𝑏𝑒𝑟 𝑜𝑓 𝑚𝑜𝑙𝑒𝑐𝑢𝑙𝑒𝑠
𝑇𝑜𝑡𝑎𝑙 𝑡𝑟𝑎𝑛𝑠𝑙𝑎𝑡𝑖𝑜𝑛𝑎𝑙
𝑒𝑛𝑒𝑟𝑔𝑦
𝑎𝑣𝑒𝑟𝑎𝑔𝑒 𝑡𝑟𝑎𝑛𝑠𝑙𝑎𝑡𝑖𝑜𝑛𝑎𝑙 𝑘𝑖𝑛𝑒𝑡𝑖𝑐
𝑒𝑛𝑒𝑟𝑔𝑦 𝑜𝑓 𝑎 𝑠𝑖𝑛𝑔𝑙𝑒 𝑚𝑜𝑙𝑒𝑐𝑢𝑙𝑒
2
2
Compare; 𝑝𝑉 = 𝑛𝑅𝑇 = 3 𝐾𝑡𝑟 → 𝐾𝑡𝑟 = 3 𝑛𝑅𝑇
Venus is just like in “Goldie
Locks” ,too hot and Mars is too
cold but earth is …
Note: H2 exceeds the escape speed. Hydrogen
as the lightest gas has an average speed at a
given temperature than other heavier gases.
Boltzmann Constant:
Escape speed 𝑣𝑎𝑠 =
2𝐺𝑚𝐸
𝑅𝐸
𝐾1 + 𝑈1 = 𝐾2 + 𝑈2
𝑠𝑢𝑟𝑓𝑎𝑐𝑒
𝑜𝑓 𝑒𝑎𝑟𝑡ℎ
𝑖𝑛𝑓𝑖𝑛𝑖𝑡𝑦
1
𝑚𝐸 𝑚
𝑚𝑣 2 + −𝐺
=0+0
2
2𝐸
𝐾𝑚𝑜𝑙𝑒𝑐𝑢𝑙𝑎𝑟 =
𝐾𝑡𝑟
𝑁
3 𝑛𝑅𝑇
𝑁
=2
3 𝑛𝑅𝑇
3
𝑅
𝐽
= 2 𝑛𝑁 = 2 𝑘𝑇  𝑘 = 𝑁 = 1.38𝑥10−23 𝑚𝑜𝑙𝑒𝑐𝑢𝑙𝑒∙𝐾
𝐴
𝐴
Clicker - Questions
You heat a sample of air to twice its original temperature in a constant
volume container. The average translational kinetic energy of the
molecules is;
A.
B.
C.
D.
Half the original value.
Unchanged.
Twice the original value.
Four time the original value.
Molecular speeds in an ideal gas
K av (molcule) 
1 2 3
mvev  kT 𝑣𝑟𝑚𝑠 =
2
2
2
𝑣𝑎𝑣
Consider O2 as residual gas at 27oC. Find
3𝑘𝑇
=
𝑚
=
𝐾𝑎𝑣
𝑝𝑒𝑟 𝑚𝑜𝑙𝑒𝑐𝑢𝑙𝑒
𝐾𝑎𝑣
3𝑅𝑇
𝑀
𝐾𝑡𝑟  27oC=300K
and
𝑝𝑒𝑟 𝑚𝑜𝑙𝑒
1
3
3
2
= 𝑚𝑣𝑎𝑣 = 𝑘𝑇 = 1.38𝑥10−23 300𝐾 = 6.21𝑥10−12 𝐽
2
2
2
3
3
𝐾𝑡𝑟 = 𝑛𝑅𝑇 = 1𝑚𝑜𝑙 (8.3) 300𝐾 = 3740𝐽
2
2
𝐽
[𝑚𝑜𝑙.𝐾]
k=1.38𝑥10−23
𝐽
[𝑚𝑜𝑙.𝐾]
Problem 15-68
(a) Find 𝑣𝑟𝑚𝑠 of the hydrogen atom for H in the sun (Tsun=5800K)
1
3
2
𝑚𝑣𝑟𝑚𝑠 = 𝑘𝑇 → 𝑣𝑟𝑚𝑠 =
2
2
3𝑘𝑇
=
𝑚
3 ∗ 1.38𝑥10−23 𝐽 ∗ 5800𝐾
𝑚
𝑘𝑚
4
= 1.2𝑥10
= 12
1.67𝑥10−27 𝑘𝑔
𝑠
𝑠
(b) What is the mass of an atom that has half the speed?
𝑣𝑟𝑚𝑠 𝑚 = 3𝑘𝑇 = 𝑐𝑜𝑛𝑠𝑡𝑎𝑛𝑡 → 𝑣𝑟𝑚𝑠,1 𝑚1 = 𝑣𝑟𝑚𝑠,2 𝑚2
1
𝑣𝑟𝑚𝑠,2 = 𝑣𝑟𝑚𝑠,1
2
𝑚2 = 4𝑚1 = 4 ∗ 1.67𝑥10−27 = 6.68𝑥10−27 𝑘𝑔
Heat capacities
Specific heat capacity (previous chapter)
1𝑐𝑎𝑙
𝑄 = 𝑚𝑡𝑜𝑡𝑎𝑙 𝑐∆𝑇  c=specific heat capacity [J/kg.K] (𝑐(𝑤𝑎𝑡𝑒𝑟) = 𝑔.𝐾 )
Molar heat capacity (novel fundamental level)
𝐽
𝑄 = 𝑛𝐶∆𝑇 → 𝐶
= 𝑚𝑜𝑙𝑎𝑟 ℎ𝑒𝑎𝑡 𝑐𝑎𝑝𝑎𝑐𝑖𝑡𝑦
𝑚𝑜𝑙. 𝐾
Related to specific heat capacity c
(small letter) by comparison with;
Molar mass
Molar heat
capacity
𝑛𝑢𝑚𝑏𝑒𝑟
𝑜𝑓 𝑚𝑜𝑙𝑒𝑠
𝑄 = 𝑚𝑡𝑜𝑡𝑎𝑙 𝑐∆𝑇 =
𝑀
𝑛
𝑐∆𝑇
𝐶 = 𝑀𝑐
Specific heat capacity
𝑚𝑜𝑙𝑎𝑟
𝑤𝑒𝑖𝑔ℎ𝑡
Change in translational kinetic energy
3
3
∆𝐾𝑡𝑟 = 𝑛𝑅∆𝑇
=
𝑛𝐶
∆𝑇
=
𝑛𝑅∆𝑇
2
𝑉
2
𝑄 = 𝑛𝐶𝑉 ∆𝑇
3
Energy gas (mono-atomic) 𝐶𝑉 = 2 𝑅
3
𝐽
𝐽
𝐶𝑉 = 8.314
= 12.47
2
𝑚𝑜𝑙. 𝐾
𝑚𝑜𝑙. 𝐾
𝑅
5
Poly-atomic: more degrees of freedom
Diatomic:  𝐶𝑉 = 2 𝑅
A diatomic molecule can move in three ways: translation, rotation, and vibration. At
lower temperature; only translation and rotation degrees are active and not vibration
Energy, heat, and work in a thermodynamic system
Work done during volume changes
s
Thermodynamics is the study of
ℎ𝑒𝑎𝑡 and
𝑊𝑜𝑟𝑘
↑
↑
𝑄 𝑎𝑑𝑑𝑒𝑑
𝑤𝑜𝑟𝑘 𝑑𝑜𝑛𝑒
(sign convection)
Thermodynamic system = exchanges heat with environment
Energy,
Work done during volume changes
The work W done is equal
to the area under the
PV curve
When gas expands, it pushes on the boundary
surfaces and does positive work.
𝑊 = 𝐹∆𝑥 = 𝑝 𝐴∆𝑥 = 𝑝∆𝑉
∆𝑉
Assume p is constant;
𝑊 = 𝑝(𝑉2 − 𝑉1 )
But usually it is not constant;
𝑊 = 𝑝1 ∆𝑉1 + 𝑝2 ∆𝑉2 … … .
Isothermal (constant temperature) expansion
(Particular case)
𝑉
𝑊 = 𝑛𝑅𝑇 ln 𝑉2 (without proof)
1
Positive work
No Work
Consider a series of paths, in such a way that each
can be plotted on a pV-diagram  they all require
different work (areas under the path)
Work done depends not only on the initial and
final points, but also on the path taken.
Work done in a cyclic process
15.39 note:
For a constant volume process: W=0
For a constant pressure process: W=p.ΔV
1 atm = 1.013x105Pa, 1Liter=10-3m3
The work done is positive when the volume increases and negative when the
volume decreases.
Find W for each process in the cycle;
12: 𝑊 = 𝑝∆𝑉 = 2.5𝑎𝑡𝑚 ∗
23: 𝑊 = 0 since ∆𝑉 = 0
𝑃𝑎
1.013𝑥105
𝑎𝑡𝑚
𝑃𝑎
1.013𝑥105 𝑎𝑡𝑚
8𝐿 − 2𝐿
3
𝑚
𝑥10−3
𝐿
= 1.5𝑥103 𝐽
3
𝑚
𝑥10−3 𝐿
34: 𝑊 = 𝑝∆𝑉 = 0.5𝑎𝑡𝑚 ∗
2𝐿 − 8𝐿
= −3.0𝑥102 𝐽
41: 𝑊 = 0 since ∆𝑉 = 0
𝑊𝑐𝑦𝑐𝑙𝑒 = 1.5𝑥103 𝐽 + 0 + −3.0𝑥102 𝐽 + 0 = 1.2𝑥103 𝐽
The area enclosed by the cycle (energy) is;
𝑚3
𝑃𝑎
−3
2𝑎𝑡𝑚 ∗ 6𝐿 ≅ 12.0 𝐿 ∙ 𝑎𝑡𝑚 ∗ 10
∗ 1.013𝑥105
= 1.2𝑥103 𝐽
𝐿
𝑎𝑡𝑚
Heat transfer during volume changes
Slow controlled isothermal expansion Rapid uncontrolled expansion
Free expansion=uncontrolled expansion
Experiments have shown that during free expansion,
there is no change in temperature. Heat also depends
on the path like work.
Q= heat of an object is not a useful concept,
better talk about internal energy U
First law of thermodynamics
+
∆𝑈
𝑊
𝑄 =
↑
↑
↑
𝐶ℎ𝑎𝑛𝑔𝑒 𝑜𝑓
𝑊𝑜𝑟𝑘 𝑑𝑜𝑛𝑒
𝐴𝑑𝑑𝑒𝑑
ℎ𝑒𝑎𝑡 𝑖𝑛𝑡𝑒𝑟𝑛𝑎𝑙 𝑒𝑛𝑒𝑟𝑔𝑦 𝑎𝑔𝑎𝑖𝑛𝑠𝑡 𝑠𝑢𝑟𝑟𝑜𝑢𝑛𝑑𝑖𝑛𝑔𝑠
Experiments show U=f(p,V,T)
𝑈2 − 𝑈1 = ∆𝑈= 𝑄 − 𝑊
𝑖𝑛𝑑𝑒𝑝𝑒𝑛𝑑𝑒𝑛𝑡 𝑜𝑓 𝑝𝑎𝑡ℎ
Example
One gram of water (1cm3) becomes 1671cm3 steam when boiled at
J
constant pressure of 1atm. The heat of vaporization is LV = 2.256x106 kg
Compute: (a) the work done by the water when it vaporizes
(b) the increase in internal energy
(a) W = p V2 − V1 = 1.013x105 Pa 1671x10−6 m3 − 1x10−6 m3 = 169 J
J
(b) Q = 𝑚Lo = 1𝑔 ∗ 2256 g = 2256 J
First law of thermodynamics: 𝑄 = ∆𝑈 + 𝑊
∆𝑈 = 𝑄 − 𝑊 = 2256 − 169 𝐽 = 2087 𝐽
Why is ∆𝑈 > W ??
Not all heat goes into internal energy but some heat does work on the
water molecules pulling them apart when water transforms into steam.
Thermodynamic processes
4 processes:
No heat transfer = Adiabatic
Constant volume = isochoric
Constant pressure = isobaric
Constant temperature = isothermal
Isothermal:∆𝑇 = 0, ∆𝑼 = 𝟎
Adiabatic:  Q=0
𝑼𝟐 − 𝑼𝟏 = 𝑸 − 𝑾
||
𝟎
Expanding system W>0, ΔU<0
Compressing system W<0, ΔU>0
Increasing internal energy is often happen with increasing temperature T
Example: combustion engine; isochoric  constant volume
𝑼𝟐 − 𝑼𝟏 = ∆𝑼 = 𝑸 − 𝑾
||
𝟎
All the energy added as heat increases energy U
Example: heating a gas in a closed volume contains;
isobaric  constant pressure
All three quantities ΔU1, W1 , and Q change.
𝑾 = 𝒑(𝑽𝟐 − 𝑽𝟏 )
Constant pressure
isobaric  constant temperature: none of the quantities ΔU1, W1 , and Q is zero.
Note that in some special case the internal energy U depends only on T  ∆𝑼 = 𝟎, 𝑄 = 𝑊 (Example 15.9)
Example 15.9 An isothermal expansion
Example 15.9
𝑊 = 𝑛𝑅𝑇𝑙𝑛
𝑉2
𝐽
5𝐿
= 3𝑚𝑜𝑙 ∗ 8.3
∗ 300𝐾 ∗ 𝑙𝑛
= 1700 𝐽
𝑉1
𝑚𝑜𝑙. 𝐾
4𝐿
Since, temperature is constant and we consider
an ideal gas the change in internal energy is
zero  all the heat entering goes into work
Example 15.10 A series of thermodynamical processes
Consider paths in a pV diagram: in path ab 150J of heat are added to the
system , in bd. 600J of heat are added. Find
a. Internal energy change in ab ?
b. Internal energy change in abd ?
c. Total heat added in acd ?
No volume change  𝑊𝑎𝑏 = 0, ∆𝑈𝑎𝑏 = 𝑄𝑎𝑏 = 150 𝐽
bd at constant pressure
𝑊𝑏𝑑 = 𝑝 𝑉2 − 𝑉1 = 8𝑥104 𝑃𝑎 5 − 2 𝑥10−5 𝑚3 = 240 𝐽
𝑊𝑡𝑜𝑡𝑎𝑙 = 𝑊𝑎𝑏 + 𝑊𝑏𝑑 = 0 + 240 = 240 𝐽
𝑄𝑎𝑏𝑑 = 𝑄𝑎𝑏 + 𝑄𝑏𝑑 = 150 + 600 = 750 𝐽
∆𝑈𝑎𝑏𝑑 = 𝑄𝑎𝑏𝑑 − 𝑊𝑎𝑏𝑑 = 750 − 240 = 510 𝐽
c) Because ΔU is independent of the path ∆𝑈𝑎𝑐𝑑 = ∆𝑈𝑎𝑏𝑑
Total work for path acd :
𝑊𝑡𝑜𝑡𝑎𝑙 = 𝑊𝑎𝑐 + 𝑊𝑐𝑑 = 𝑝 𝑉2 − 𝑉1 + 0 = 3𝑥104 𝑃𝑎 5 − 2 𝑥10−3 𝑚3 = 90 𝐽
a)
b)
Problem on Heat Capacities
a) How much heat does it take to increase the temperature of 2.5moles of an ideal
gas (monoatomic) from 25oC to 55oC, if the gas is at constant volume.
b) How much heat is needed if the gas is diatomic rather than monoatomic?
c) Sketch in a pV-diagram of these processes.
3
𝐽
a) 𝑄 = 2.5𝑚𝑜𝑙 2 8.315 𝑚𝑜𝑙.𝐾 𝐶 30𝐾 = 935𝐽
5/2
𝐽
R= 8.315 𝑚𝑜𝑙.𝐾 𝐶
b) 𝑄 = 3/2 ∗ 935 = 1560 𝐽
c)
Isochoric = when the temperature increases at
constant volume the pressure increases
Clicker - Questions
You compress a sample of air slowly to half its original volume,
keeping its temperature constant. The internal energy of the gas.
A. Decreases to half its original value.
B. Remains unchanged.
C. Increases to twice its original value.
Properties of an ideal gas:Heat capacities and the adiabatic process
Free expansion: When the partition is broken the gas
expands freely into the vacuum region. Internal energy
stays constant and temperature does not change
Molar heat capacity depends on condition under which heat is added.
𝐶𝑉 = heat is added to raise temperature 𝑄 = ∆𝑈 under constant volume, but letting
pressure go up.
𝐶𝑝 = heat is added while gas expands 𝑄 = ∆𝑈 + 𝑊 but keeping pressure constant.
Adiabatic: Q=0
𝛾
𝛾
𝑝1 𝑉1 = 𝑝2 𝑉2 = 𝑐𝑜𝑛𝑠𝑡𝑎𝑛𝑡𝛾 =
𝐶𝑝
𝐶𝑉
Isothermal: ΔT=0
𝑝1 𝑉1 = 𝑝2 𝑉2 = 𝑛𝑅𝑇
Walls of container
do not move
𝐽
Note: 𝐶𝑝 = 𝐶𝑉 + 𝑅 where 𝑅 = 8.314 𝑚𝑜𝑙.𝐾
Clicker - Questions
The gas shown in figure is in a completely insulated rigid container.
Weight is added to the frictionless piston, compressing the gas. As this
is done,
A. The temperature of the gas stays the
same because the container is
insulated.
B. The temperature of the gas
increases because heat is added to
the gas.
C. The temperature of the gas
increases because work is done on
the gas.
D. The pressure of the gas stays the
same because the temperature of the
gas is constant.
Problem 15 - 79
Note: ab isochoric (constant volume)
bc isothermic (constant temperature)
ca isobaric (constant pressure)
For;
∆𝑇 = 0 → ∆𝑈 = 0
𝑉
𝑄 = 𝑊 = 𝑛𝑅𝑇𝑙𝑛 𝑉𝑐 (isotherm)
𝑄 = ∆𝑈 + 𝑊
𝑏
5
𝐶𝑉 = 𝑅 (diatomic gas)
2
7
𝐽
𝐶𝑝 = 𝐶𝑉 + 𝑅 = 2 𝑅 (R=8.315𝑚𝑜𝑙.𝐾)
∆𝑈 = 𝑛𝐶𝑉 ∆𝑇
pV-diagram for 0.004mole of ideal H2 gas
(a) What is the volume at c ?
temperature does not change during path bc.
𝑇𝑏 = 𝑇𝑐  for states b and c
𝑝𝑉 = 𝑛𝑅𝑇 → 𝑝𝑏 𝑉𝑏 = 𝑝𝑐 𝑉𝑐
𝑝𝑏
2
𝑉𝑐 = 𝑉𝑏
= 0.2 ∗
= 0.8 𝐿
𝑝𝑐
0.5
(b) Find temperature of the gas at points ab and c
𝑇𝑎 =
𝑝𝑎 𝑉𝑎
𝑛𝑅
𝑃𝑎
=
(0.5 𝑎𝑡𝑚)(1.013𝑥105 𝑎𝑡𝑚)(0.2𝑥10−3 𝑚3 )
𝐽
0.004𝑚𝑜𝑙∗8.315𝑚𝑜𝑙.𝐾
𝑇
𝑉
𝑁
= 305𝐾 (Note: 𝑝𝑎 = 𝑚2)
𝑇
𝑇
𝑉𝑎 = 𝑉𝑏  for states a and b  𝑝 = 𝑛𝑅 = 𝑐𝑜𝑛𝑠𝑡𝑎𝑛𝑡 → 𝑝𝑎 = 𝑝𝑏
𝑎
𝑏
𝑝𝑏
2
𝑇𝑏 = 𝑇𝑐 = 𝑇𝑎
= 305 ∗
= 1220𝐾
𝑝𝑎
0.5
Continued on next slide
(c) How much heat went into or out of the gas during segments ab, ca and bc ?
3
3
𝐽
∗
8.315
1220 − 305 𝐾 = +76 𝐽
2
𝑚𝑜𝑙.𝐾
7
7
𝐽
𝑛𝐶𝑝 ∆𝑇 = 𝑛 2 𝑅∆𝑇 = 0.004𝑚𝑜𝑙 2 ∗ 8.315 𝑚𝑜𝑙.𝐾 305 − 1220 𝐾 = −107 𝐽
𝑉
𝐽
0.8 𝐿
𝑊 = 𝑛𝑅𝑇 = 𝑛𝑅𝑇𝑙𝑛 𝑉𝑐 = 0.004𝑚𝑜𝑙 ∗ 8.315 𝑚𝑜𝑙.𝐾 1220𝐾 ∗ ln(0.2 𝐿) = +56
𝑏
ab: 𝑄 = 𝑛𝐶𝑉 ∆𝑇 = 𝑛 2 𝑅∆𝑇 = 0.004𝑚𝑜𝑙
ca: 𝑄 =
bc: 𝑄 =
𝐽
(d) Find the change in the internal energy of this hydrogen during segments ab, ca and
bc ?
5
ab: ∆𝑈 = 𝑛𝐶𝑉 ∆𝑇 = 𝑛 2 𝑅∆𝑇 = 0.004𝑚𝑜𝑙
7
5
2
𝐽
∗ 8.315 𝑚𝑜𝑙.𝐾 1220 − 305 𝐾 = +76 𝐽
ca: ∆𝑈 = 𝑝 𝑉𝑐 − 𝑉𝑎 + 𝑛 2 𝑅∆𝑇
= 0.5 ∗ 1.013 ∗ 105 0.8 − 0.2 ∗ 10−3 + 0.004𝑚𝑜𝑙
= −76 𝐽
bc: ∆𝑇 = 0 → ∆𝑈 = 0
7
𝐽
∗ 8.315
305 − 1220 𝐾
2
𝑚𝑜𝑙. 𝐾
Note: the net energy change in a cycle is zero. ∆𝑈𝑡𝑜𝑡𝑎𝑙 = +76 + 0 − 76 = 0
factors of unity
1 atm = 1.013x105 Pa
1 m3 = 103 L